The ionization energy of α-sexithiophene and p -sexiphenyl in 2D and 3D thin films grown on silicon oxide surfaces.

The ionization energy (IE) of molecular thin films is sensitive to the molecular environments surrounding ionized molecules. In this study, we investigate the evolution of the IE on dimension-controlled 2D and 3D thin films of rod-like molecules, namely α-sexithiophene (α-6T) and p -sexiphenyl ( p -6P), grown on SiO 2 surfaces via photoelectron yield spectroscopy. In 2D thin films, the IE of α-6T and p -6P showed nearly constant values of 4.93 eV and 5.50 eV, respectively. In 3D thin films, however, with increasing coverage, the IE of the α-6T thin films gradually decreased to 4.84 eV at 15 ML (ML: monolayer) and the IE of the p -6P thin films gradually increased to 5.65 eV at 7 ML. These experimental findings underline the less significant impact of the domain size on the IE in 2D thin films and the significant impact of the neighboring layers on the IE in 3D thin films.